JP6502339B2 - Novel catalysts with silylene ligands - Google Patents

Description

  The present invention relates to new types of metal complexes which can be used as catalysts, in particular as hydrosilylation catalysts. More specifically, the present invention relates to metal complexes having at least one silylene-type ligand.

  During the hydrosilylation (also known as polyaddition) reaction, the compound containing at least one unsaturation is reacted with the compound containing at least one hydrosilyl function, ie a hydrogen atom is attached to the silicon atom. This reaction is, for example, in the case of an alkene type

In the case of alkyne-type unsaturation,

Can be explained by
The hydrosilylation of unsaturated compounds is carried out catalytically. Typically, a suitable catalyst for this reaction is a platinum catalyst. At present, most of the industrial hydrosilylation reactions can be performed with Karstedt platinum complexes of the general formula Pt ₂ (divinyl tetramethyldisiloxane) ₃ (or Pt ₂ (DVTMS) _{3 for} short):

It is catalyzed by
At the beginning of the 2000s, the general formula:

The preparation of the platinum-carbene complex of (H) allowed the use of a more stable catalyst (see, for example, US Pat. No. 5,956,015).
However, the use of platinum catalysts is still problematic. This relates to expensive metals that are becoming more scarce, and their costs vary widely. Its use on an industrial scale is difficult. Therefore, it is desirable to reduce the amount of catalyst needed for the reaction as much as possible, but not reduce the yield and reaction rate.

  Furthermore, it is desirable to be able to use a stable catalyst during the reaction. It has been found that, during the catalyzed reaction, metallic platinum can precipitate out and form insoluble colloids in the reaction medium. The catalyst is therefore not active. Furthermore, these colloids form turbidity in the reaction medium and the resulting product is colored and is not aesthetically pleasing.

  Furthermore, during the Karstedt-catalyzed hydrosilylation reaction, the formation of undesired by-products resulting from the isomerization of olefinic double bonds and / or the hydrogenation reaction has been observed. It is also desirable that the catalyst not promote side reactions.

  In such circumstances, one of the objects of the present invention is to provide a new type of catalyst which is particularly suitable for catalyzing hydrosilylation reactions. Advantageously, this catalyst can be used in smaller amounts than existing catalysts while maintaining the same effectiveness. Furthermore, the novel catalysts can advantageously be stable in the reaction medium, do not form colloids and make it possible to limit side reactions.

  During these exploration studies, we were interested in metal complexes with silylene ligands. Silylene is a chemical compound that is a higher homologue of carbene. These are divalent neutral silicon entities with six valence electrons. In contrast to carbene, the number of stable silylenes described in the literature is very limited. N-heterocyclic silylene NHSi, a higher homolog of N-heterocyclic carbene NHC, is the most studied, and silylene NHSi is found to form a much more labile complex than the complex formed by NHC. It is done.

  In order to solve this problem we suggest the use of silylene ligands stabilized by Lewis bases. Several stable metal complexes coordinated by a silylene ligand stabilized by a Lewis base are described in the literature, in particular in [1].

However, the complexes described are still not very stable and stability problems are observed in these publications.
Under such circumstances, the present inventors have prepared for the first time metal complexes in which at least one of the ligands is a cyclic silylene compound stabilized by a Lewis base. We have found, quite surprisingly, that these stabilized silylene ring structures give particularly stable metal complexes.

WO01 / 42258 US Patent Application No. 2009/0182099 U.S. Patent Application No. 2009/0182091 French Patent No. 1528464 French Patent No. 2372874

R. Rodriguez, T .; Troadec, T .; Kato, N .; Saffon-Merceron, J-M. Sotiropoulos, and A. Baceiredo, Angew. Chem. Int. Ed. , 2012, 51, 7158

  The subject of the present invention is a metal complex comprising at least one metal atom selected from metals of groups 8, 9 and 10 of the Periodic Table of the Elements and one or more ligands, wherein the at least one ligand is a ring It is characterized by including a formula silylene structure and a Lewis base which gives an electron pair to a silicon atom of the cyclic silylene structure.

These metal complexes are particularly suitable for use as catalysts, which are also the subject of the present invention.
Furthermore, another subject of the invention is a process for the hydrosilylation of unsaturated compounds, which comprises at least one alkene function and / or at least one alkyne function, with a compound which comprises at least one hydrosilyl function. Said method is characterized in that it is catalyzed by a metal complex as defined above, and the other is:
At least one unsaturated compound comprising at least one alkene function and / or at least one alkyne function,
A catalyst selected from at least one compound comprising at least one hydrosilyl function, and a metal complex as defined above,
A composition comprising

According to a first aspect, the present invention is a metal complex comprising at least one metal atom selected from metals of Groups 8, 9 and 10 of the Periodic Table of the Elements, and one or more ligands, One ligand relates to a metal complex characterized in that it comprises a cyclic silylene structure and a Lewis base that donates an electron pair to a silicon atom of the cyclic silylene structure.
This metal complex has the general formula (I):
[M _a (Lig) _b ] ^c (I)
Can be represented by
During the ceremony:
M represents a metal selected from metals of Groups 8, 9 and 10 of the Periodic Table of the Elements;
The symbol Lig represents a ligand of metal M;
-A is 1, 2 or 3;
B is an integer in the range of numbers equal to 5 times the number 1 to a;
C corresponds to the total charge of the metal complex, which may be a positive integer in the range of 0 or +1 to +6;
It is understood that when b is 2 or more, Lig can represent the same or different ligand,
At least one ligand Lig is characterized in that it is a ligand comprising a cyclic silylene structure and a Lewis base for donating an electron pair to a silicon atom of the silylene structure.

  In the present invention, metals of Groups 8, 9 and 10 of the Periodic Table of the Elements are iron (Fe), ruthenium (Ru), osmium (Os), hashium (Hs), cobalt (Co), rhodium (Rh), Iridium (Ir), Mitnerium (Mt), Nickel (Ni), Palladium (Pd), Platinum (Pt), and Dermstatium (Ds). Preferably, the metal of the metal complex according to the invention is the group consisting of Pt, Pd, Ni, Rh, Ru, Os and Ir, more preferably the group consisting of Pt, Pd, Ni, Rh and Ru, even more preferably Is selected from the group consisting of Pt, Pd, and Ru. Most preferably, the metal is Pt and the metal complex of the invention is a platinum complex.

  The complex can contain only one metal atom, which means that in the general formula (I) the symbol "a" is the number 1. However, it is also possible that the metal complex comprises several metal atoms, in particular if at least one of the ligands of the complex is a bridging or multidentate ligand.

  Although the metal complex according to the present invention is neutral (which means that the symbol “c” in the general formula (I) has a numerical value of 0), the charge (in the general formula (I), the symbol “c” is also zero) And may be numerical values +1, +2, +3, +4, +5, or +6). In the latter case, the metal complex can be associated with one or more counterions.

One or more ligands complex one or more metal atoms. The metal complex according to the present invention is characterized in that at least one ligand comprises a cyclic silylene structure and a Lewis base which donates an electron pair to a silicon atom of the cyclic silylene structure. Hereinafter, this ligand is referred to as "L _S ".

  The silylene compound is a chemical compound that is electrically neutral and contains a divalent silicon atom at which two non-bonded electrons are located. Conventionally, silylene compounds are

Can be represented by the symbol:

Indicates that the electron is empty, and the symbol:

Represents a non-bonded electron.
The term "cyclic silylene structure" is understood to mean silylene compounds in which the divalent silicon atom forms part of a ring consisting of 3 to 6 atoms linked via a covalent bond. The cyclic silylene structure is schematically:

And a silicon atom and two substituents bonded to the silicon atom are contained in a ring composed of 3 to 6 atoms bonded to each other via a covalent bond.
The term "Lewis base" is understood to mean a chemical group capable of providing an electron pair. Customarily, Lewis bases are

Can be represented by the symbol:

Represents an electron pair. In the present invention, the Lewis base of the ligand donates its electron pair to the silicon atom of the cyclic silylene structure. This is schematically:

Or more conveniently

Can be represented by
Among the ligands comprising a cyclic silylene structure and a Lewis base as described above, L _S is a compound of formula (II):

Can be a compound of
During the ceremony:
-B represents a Lewis base,
Y ¹ and Y ² independently of one another represent O, NR ^a or CR ^a ₂ ,
Z is such that Y ¹ -Z-Y ² together form a Y ^1- (CR ^a _m ) _n -Y ² chain, n is 0, 1, 2 or 3 Wherein each m is independently 0, 1 or 2 and one or more carbon atoms of this chain can be substituted with a heteroatom selected from O, N, Si and P It is understood that this chain can contain one or more unsaturations and that the number m of R ^a groups carried by each atom of the chain is suitable for the coordination of this atom And
B is capable of binding to Y ¹ , Y ² and / or Z via a covalent bond,
And each ^Ra is:
-Hydrogen atom,
-Halogen atom,
-An alkyl group optionally substituted by one or more halogen atoms, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-A cycloalkyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Desired in the cycloalkyl moiety and / or the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group And cycloalkylalkyl groups substituted by one or more
An aryl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Optionally in the aryl and / or alkyl moiety by means of a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group One or more substituted arylalkyl groups,
-An acyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-Hydroxyl group,
-Optionally substituted one or more in the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group An alkoxy group,
An amine group optionally substituted by one or more halogen atoms, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group; Imine group or amido group; and-optionally by a halogen atom, alkyl group, haloalkyl group, cycloalkyl group, cycloalkyl group, cycloalkyl group, aryl group, arylalkyl group, acyl group, amine group, hydroxyl group, or alkoxy group; Phosphine group, phosphorous group, phosphorane group, or phosphorus ylide group, which is substituted as above
Can be independently selected from
In each R ^a group, one or more carbon atoms can be replaced by the silicon atom Si,
One or more unsaturations can be present in each R ^a group,
Two or more groups selected from R ^a groups, optionally together with the atoms to which they are attached, optionally one or more unsaturations, and one or more different species selected from O, N, Si, and P A 3- to 20-membered monocyclic or polycyclic ring optionally containing an atom can be formed, and the monocyclic or polycyclic ring group is a halogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, It may be optionally substituted one or more by an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group,
It is to be understood.

The term "halogen atom" is understood according to the invention to mean an atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
The term "alkyl" is understood according to the invention to mean a saturated straight or branched hydrocarbon chain containing 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. . The alkyl group can be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl.

  The term "cycloalkyl" according to the present invention is a saturated monocyclic or polycyclic, preferably monocyclic, containing from 3 to 20 carbon atoms, preferably from 3 to 8 carbon atoms. It is understood to mean a bicyclic hydrocarbon group. When the cycloalkyl group is polycyclic, the polycyclic nuclei can be connected to one another via covalent bonds and / or spiro atoms and / or fused to one another. The cycloalkyl group can be selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl and norbornyl.

  The term "cycloalkylalkyl" is understood according to the invention to mean an alkyl group as defined above, substituted by a cycloalkyl group as further defined above.

  The term "aryl" is understood according to the invention to mean an aromatic monocyclic or polycyclic hydrocarbon group containing 5 to 18 carbon atoms. The aryl group can be selected from the group consisting of phenyl, naphthyl, anthracenyl and phenanthryl.

The term "arylalkyl" is understood according to the invention to mean an alkyl group as defined above, substituted by a cycloalkyl group as further defined above.
The term "acyl" is understood according to the invention to mean an alkyl, cycloalkyl or aryl group as defined above attached to a C = O group.

  The term "alkoxy" is understood according to the invention to mean an alkyl group as defined above attached to an oxygen atom. The alkoxy group can be selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

  The term "amine" is understood according to the invention to mean a primary amine group or a second, third or quaternary amine group, these substituents being derived from an alkyl group as defined above. It is selected.

In the above formulae, Y ¹ and Y ² are preferably CR ^a ₂ .
Furthermore, in the above formulae, n is preferably 0 or 1.
According to a preferred embodiment, the cyclic silylene structure of L 2 _S is electrically neutral from the three atoms to which the divalent silicon atom at which the two non-bonded electrons are located is linked via a covalent bond. And a silylene compound forming part of the ring. Among these three atoms that constitute the ring, one is a silylene type silicon atom and the other two can be selected from C, N and O. Specifically, L _S can be a compound of formula (II) as defined above, where the symbol n is the number 0. In this case, Z represents a covalent bond. L _S is a group of formula (IIa):

And B, Y ¹ and Y ² have the meanings given above.
Highly preferably, the cyclic silylene structure is a silacyclopropylidene, ie a 3-membered ring formed by a silylene-type silicon atom and two carbon atoms:

It is.
More specifically, L _S has the formula (III):

Can be a compound of
During the ceremony:
B represents a Lewis base;
Each R ^b is:
-Hydrogen atom,
-Halogen atom,
-An alkyl group optionally substituted by one or more halogen atoms, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-A cycloalkyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Desired in the cycloalkyl moiety and / or the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group And cycloalkylalkyl groups substituted by one or more
An aryl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Optionally in the aryl and / or alkyl moiety by means of a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group One or more substituted arylalkyl groups,
-An acyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-Hydroxyl group,
-Optionally substituted one or more in the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group An alkoxy group,
An amine group optionally substituted by one or more halogen atoms, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group; At least one group selected from groups or amide groups, and-halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups A substituted phosphine group, a phosphite group, a phospholane group, or a phosphorus ylide group,
Can be selected independently from;
In each R ^b group, one or more carbon atoms can be replaced by the silicon atom Si;
One or more unsaturations may be present in each R ^b group;
Two or more groups selected from R ^b groups, optionally together with the atoms to which they are attached, optionally one or more unsaturations, and one or more different species selected from O, N, Si, and P A 3- to 20-membered monocyclic or polycyclic ring optionally containing an atom can be formed, and the monocyclic or polycyclic ring group is a halogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, It may be optionally substituted one or more by an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group,
Is to be understood,
And B can be attached to one or more R ^b groups via a covalent bond.

Preferably, in ligand L _S , Lewis base B is carbon monoxide (CO), water (H ₂ O), alcohol (-OH), ether (-O-), thiol (-SH), sulfide (-S) -), Selected from the group consisting of phosphine (-P <), phosphoalkene (-P =), phosphoalkyne (PN), amine (-N <), imine (-N =), and nitrile (N≡) And preferably is selected from the group consisting of sulfide (-S-), phosphine (-P <), phosphoalkene (-P =), amine (-N <), and imine (-N =) .

  In particular, Lewis base B is:

And each R ^c independently represents a hydrogen atom, a halogen atom, or: an alkyl group optionally substituted by one or more halogen atoms and / or an alkyl group, a haloalkyl group, a cycloalkyl A cycloalkyl alkyl group optionally substituted by one or more halogen atoms and / or an alkyl group, a cycloalkyl moiety and / or an alkyl portion; an aryl optionally substituted by a halogen atom and / or an alkyl group A group selected from the group consisting of an arylalkyl group which is optionally substituted one or more at a aryl moiety and / or an alkyl moiety with a halogen atom and / or an alkyl group; an acyl group; an amine group; and a hydroxyl group.

In one aspect of the invention, the cyclic silylene structure and the Lewis base contained in the ligand L _S are linked only via the donor coordination that occurs between the Lewis base and the silylene type silicon atom. According to another aspect, the Lewis base contained in the ligand L _S is attached to at least one atom of the cyclic silylene structure other than the silylene type silicon atom. This means that the cyclic silylene structure and the Lewis base are linked via a covalent bond in addition to the donor coordination that occurs between the Lewis base and the silylene-type silicon atom. In this case, Lewis base B is preferably alcohol (-OH), ether (-O-), thiol (-SH), sulfide (-S-), phosphine (-P <), phosphoalkene (-P =) , Phosphoalkyne (-P≡), amine (-N <), imine (-N =), and nitrile (N≡), more preferably sulfide (-S-), phosphine (-P <), It is selected from the group consisting of phosphoalkenes (-P =), amines (-N <), and imines (-N =). In particular, the ligand L _S has the formula (IV):

Can be a compound of
In which each R ^b is independently as described above,
-R ^d -B is:
-An alkyl group optionally substituted by one or more halogen atoms, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-A cycloalkyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Desired in the cycloalkyl moiety and / or the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group And cycloalkylalkyl groups substituted by one or more
An aryl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
Optionally in the aryl and / or alkyl moiety by means of a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group One or more substituted arylalkyl groups,
-An acyl group optionally substituted by one or more halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups,
-Optionally substituted one or more in the alkyl moiety by a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group An alkoxy group,
An amine group optionally substituted by one or more halogen atoms, an alkyl group, a haloalkyl group, a cycloalkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group; At least one group selected from groups or amide groups, and-halogen atoms, alkyl groups, haloalkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, arylalkyl groups, acyl groups, amine groups, hydroxyl groups, or alkoxy groups A substituted phosphine group, a phosphite group, a phospholane group, or a phosphorus ylide group,
A radical obtained by substituting B with a group selected from
B:
Halogen atoms, or: alkyl groups optionally substituted one or more by halogen atoms and / or alkyl groups, haloalkyl groups, cycloalkyl groups; halogen atoms and / or alkyl groups, desired in cycloalkyl moieties and / or alkyl moieties A cycloalkyl alkyl group substituted by one or more; an aryl group optionally substituted by one or more halogen atoms and / or an alkyl group; one or more optionally in an aryl moiety and / or an alkyl moiety by a halogen atom and / or an alkyl group A substituted arylalkyl group; an acyl group; and a sulfide optionally substituted by a group selected from a hydroxyl group;
Halogen atoms, or: alkyl groups optionally substituted one or more by halogen atoms and / or alkyl groups, haloalkyl groups, cycloalkyl groups; halogen atoms and / or alkyl groups, desired in cycloalkyl moieties and / or alkyl moieties A cycloalkyl alkyl group substituted by one or more; an aryl group optionally substituted by one or more halogen atoms and / or an alkyl group; one or more optionally in an aryl moiety and / or an alkyl moiety by a halogen atom and / or an alkyl group A substituted arylalkyl group; an acyl group; and a phosphine optionally substituted by a group selected from a hydroxyl group;
Halogen atoms, or: alkyl groups optionally substituted one or more by halogen atoms and / or alkyl groups, haloalkyl groups, cycloalkyl groups; halogen atoms and / or alkyl groups, desired in cycloalkyl moieties and / or alkyl moieties A cycloalkyl alkyl group substituted by one or more; an aryl group optionally substituted by one or more halogen atoms and / or an alkyl group; one or more optionally in an aryl moiety and / or an alkyl moiety by a halogen atom and / or an alkyl group A substituted arylalkyl group; an acyl group; and a phosphoalkene optionally substituted by a group selected from a hydroxyl group;
Halogen atoms, or: alkyl groups optionally substituted one or more by halogen atoms and / or alkyl groups, haloalkyl groups, cycloalkyl groups; halogen atoms and / or alkyl groups, desired in cycloalkyl moieties and / or alkyl moieties A cycloalkyl alkyl group substituted by one or more; an aryl group optionally substituted by one or more halogen atoms and / or an alkyl group; one or more optionally in an aryl moiety and / or an alkyl moiety by a halogen atom and / or an alkyl group A substituted aryl alkyl group; an acyl group; and an amine optionally substituted by a group selected from a hydroxyl group; and-a halogen atom, or: at least one optionally substituted by a halogen atom and / or an alkyl group A cycloalkyl group optionally substituted with one or more substituents in the cycloalkyl moiety and / or alkyl moiety by a halogen atom and / or an alkyl group; and optionally, a halogen atom and / or an alkyl group One or more substituted aryl groups; an arylalkyl group optionally substituted by one or more at the aryl moiety and / or the alkyl moiety by a halogen atom and / or an alkyl group; an acyl group; and an optionally selected one from a hydroxyl group Substituted imines,
Is a group selected from

In particular, the ligand L _S has the formula (V):

Can be a compound of
Wherein each R ^b is independently as described above, and each R ^e is independently optionally substituted one or more with a hydrogen atom, a halogen atom, or: a halogen atom and / or an alkyl group Alkyl group, haloalkyl group, cycloalkyl group; cycloalkyl alkyl group optionally substituted by one or more at a cycloalkyl moiety and / or alkyl moiety by a halogen atom and / or an alkyl group; desired by a halogen atom and / or an alkyl group A group selected from an aryl group substituted by one or more; an arylalkyl group optionally substituted by one or more at an aryl part and / or an alkyl part by a halogen atom and / or an alkyl group; an acyl group; and a hydroxyl group ,
Alternatively, the two or more groups selected from R ^e and R ^b groups, optionally together with the atoms to which they are attached, optionally contain one or more unsaturations, and are selected from O, N, Si, and P A 3- to 20-membered monocyclic or polycyclic ring optionally containing one or more hetero atoms can be formed, and the monocyclic or polycyclic ring group is a halogen atom, an alkyl group, a cycloalkyl group, a cyclo It may be optionally substituted one or more by an alkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group.

Very specifically, the ligand L _S has the formula (VI):

Can be a compound of
In the formula, the symbol "Q" is

And the symbol "Ary" is

Represents
In all cases, if the ligand L _S contains an asymmetric atom (especially a carbon, nitrogen or phosphorus atom), L _S is a pure isomer, eg an enantiomer or diastereoisomer, or an isomer It may be a mixture, in particular a racemic mixture. Making the ligand L 2 _S available in the form of pure isomers may be particularly advantageous as metal complexes containing this ligand have advantageous properties in asymmetric synthesis and catalysis.

Ligands L _S comprising a cyclic silylene structure and a Lewis base which donates an electron pair to the silicon atom of said cyclic silylene structure are specifically photolyzed by methods conventionally used to prepare silylene compounds, It can be prepared by pyrolysis or reduction.

The ligand L 2 _S can be prepared from a precursor comprising a cyclic dihalosilane structure and a Lewis base which donates an electron pair to the silicon atom of said cyclic dihalosilane structure. The cyclic dihalosilane structure contains at least one ring consisting of 3 to 6 atoms linked via a covalent bond, at least one of these atoms being two halogen atoms, preferably two chlorines or bromines It is a tetravalent silicon atom bonded to an atom, more preferably two chlorine atoms. Precursors of ligand L _S are schematically shown:

And the symbol “X” independently of one another preferably represents a halogen atom selected from chlorine and bromine, preferably chlorine. The precursors can be prepared conventionally by synthetic routes known to those skilled in the art. The ligand L 2 _S can be prepared by reduction of the precursor as defined above using an alkali metal or alkaline earth metal such as potassium, sodium, lithium or magnesium. For example, it is possible to carry out the reduction of the precursor using magnesium powder in a solvent at ambient temperature. This reduction reaction is schematically:

Can be represented by
Alternatively, the ligand L _S can be prepared from a Lewis base stabilized acyclic silylene compounds, which are converted to cyclic silylene compounds.

The metal complexes which are the subject of the present invention comprise at least one metal atom selected from metals of groups 8, 9 and 10 of the Periodic Table of the Elements and at least one ligand L _{S as} defined above. . In this metal complex, the complexation of the metal atom by the ligand L 2 _S takes place via a silylene-type silicon atom. The metal complex can comprise only one ligand L _S or several ligands L _S. If several ligands L _S are present, these may be identical or different. Furthermore, the metal complexes according to the invention can comprise one or more other ligands. The number and nature of the ligands are appropriate to the charge of the metal atom.

  Preferably, the metal complexes according to the invention are, independently of one another, carbon monoxide, phosphines, amines, molecular hydrogen, halogens, carboxylate ions, sulfonate ions, amide radicals, alkoxide radicals, acetylacetonate radicals, 1 to 7 And alkyl radicals having 3 carbon atoms, nitrogen monoxide, nitriles, isonitriles, mono- and di-olefins, alkynes, and one or more other ligands selected from the group consisting of aromatic radicals. The ligands can be monodentate or multidentate, in particular bidentate, tridentate or tetradentate.

  The metal complexes according to the invention have the formula:

Of divinyl tetramethyl disiloxane (DVTMS) can be included as a ligand.
According to a very specific aspect, the metal complex is of the formula (VII):

A compound of
In the formula, the symbol "Q" is

And the symbol "Ary" is

Represents
Metal complexes according to the invention, by ligand exchange from the most advanced known complexes, i.e., can be prepared by adding at least one ligand L _S to a suitable precursor metal complexes in solution. The precursor metal complexes can in particular be selected from metal complexes with divinyl ligands, metal complexes with cyclooctadiene ligands, and metal complexes with olefin and bisphosphine ligands. Preferably, the precursor metal complex is selected from a metal complex of formula M (COD) _{2 and} a metal complex of formula M ₂ (DVTMS) ₃ and "M" is a group 8, 9, and 10 of the periodic table of elements And “COD” represents a cycloocta-1,5-diene ligand, and “DVTMS” represents a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligand. Most preferably, the precursor metal complex is Karstedt platinum complex Pt ₂ (DVTMS) ₃ .

  Metal complexes as described above are particularly advantageous because they are stable. The use of these metal complexes as catalysts is the subject of the present invention. In particular, they can be catalysts of reactions known to the person skilled in the art that they can be catalyzed by organometallic catalysts with ligands of the carbene type. The invention also relates to a catalyst comprising at least one metal complex as described above, and a method for carrying out a chemical reaction characterized in that the reaction is catalyzed by one of these metal complexes. .

  The subject matter of the present invention very particularly relates to compounds containing at least one hydrosilyl (≡Si-H) function of an unsaturated compound containing at least one alkene function and / or at least one alkyne function. A hydrosilylation process characterized in that it is catalyzed by a metal complex as defined above. In this method, the metal complex is preferably a platinum complex.

  The inventors have quite unexpectedly found that the metal complexes according to the invention are as efficient as the conventionally used catalysts such as the Karstedt catalyst while using small amounts of catalysts such as hydrosilylation reactions And, in some cases, have been found to be more efficiently catalyzed. This result is particularly advantageous as the catalyst concentration in the reaction medium and thus the platinum concentration can be reduced without affecting the reaction yield. Furthermore, during the use of these catalysts, no formation of colloids was observed and formation of by-products was not promoted, in fact even reduced, compared to those obtained with conventionally used catalysts such as Karstedt's catalyst .

  According to a first aspect, the compound comprising at least one hydrosilyl functional group is a silane or polysilane compound comprising at least one hydrogen atom bonded to a silicon atom. A "silane" compound is understood in the present invention to mean a chemical compound comprising a silicon atom linked to four hydrogen atoms or organic substituents. A "polysilane" compound is understood in the present invention to mean a chemical compound having at least one ≡Si-Si≡ unit.

According to a second aspect, the compound comprising at least one hydrosilyl functional group is a siloxane compound comprising at least one hydrogen atom bonded to a silicon atom. A "siloxane" compound is understood in the present invention to mean a chemical compound having at least one ≡Si-O-Si≡ unit. The siloxane compound contains at least two silicon atoms, preferably at least three or more silicon atoms. Said siloxane compound is advantageously of formula (VIII)
H _d U _e SiO _{(4- (d + e)) / 2} (VIII)
[In the formula:
-U represents a monovalent radical other than a hydrogen atom,
D and e represent integers, d is a number 1 or 2, e is a number 0, 1 or 2 and (d + e) is a number 1, 2 or 3]
At least one unit of and optionally, formula (IX):
U _f SiO _{(4-f) / 2} (IX)
[Wherein, U has the same meaning as described above, and f represents an integer of 0 to 3]
Can be a polyorganosiloxane (usually denoted as POS) containing other units of

It is understood that in the above formulas (VIII) and (IX), when several U groups are present, they may be identical to or different from one another.
In formula (VIII), the symbol d can preferably be of value 1.

Furthermore, in Formula (VIII) and Formula (IX), U is selected from the group consisting of an alkyl group having 1 to 8 carbon atoms optionally substituted by at least one halogen atom, and an aryl group Can represent a radical of valence. U can conveniently represent a monovalent radical selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl. Examples of units of formula (VIII), the _{following: H (CH 3) 2 SiO} 1/2, HCH 3 SiO 2/2, and _{H (C} 6 _{H 5)} is as _{SiO 2/2.}

Polyorganosiloxanes can exhibit linear, branched, cyclic or network structures.
Examples of polyorganosiloxanes which may be siloxane compounds containing at least one hydrogen atom bonded to a silicon atom are:
-Poly (dimethylsiloxane) having a hydrodimethylsilyl end;
-Poly (dimethylsiloxane-co-methylhydrosiloxane) having a trimethylsilyl end;
-Poly (dimethylsiloxane-co-methylhydrosiloxane) having a hydrodimethylsilyl end;
-Poly (methylhydrosiloxane) having a trimethylsilyl end; and-cyclic poly (methylhydrosiloxane),
It is.

  Preferably, the compound comprising at least one hydrosilyl functional group is a polyorganosiloxane compound comprising at least two hydrosilyl (Si-H) functional groups per molecule.

  Finally, according to a third aspect, the compound comprising at least one hydrosilyl function is an organic polymer comprising a hydrosilyl function at the terminal position. The organic polymer can be, for example, polyoxyalkylene, saturated hydrocarbon polymer, or poly (meth) acrylate. Organic polymers containing reactive functional groups at the terminal site are described in particular in US Pat.

  The second reactant of the hydrosilylation reaction is an unsaturated compound. An unsaturated compound according to the present invention is a chemical compound comprising at least one unsaturation which does not form part of an aromatic ring. Unsaturated compounds contain at least one alkene function and / or one alkyne function. Any compound containing at least one alkene function and / or one alkyne function may be used in the process according to the invention, as long as it does not contain reactive chemical functions that may mask or even interfere with the hydrosilylation reaction. it can.

  According to one aspect, the unsaturated compound comprises one or more alkene functional groups and 2 to 40 carbon atoms. According to another aspect, the unsaturated compound comprises one or more alkyne functional groups and 2 to 40 carbon atoms.

The unsaturated compounds are preferably acetylene, C ₁ -C ₄ alkyl acrylates and methacrylates, acrylic acid or methacrylic acid, alkenes, preferably octene, more preferably 1-octene, allyl alcohol, allylamine, allyl glycidyl ether, piperidine Allyl ethers, preferably allyl ethers of sterically hindered piperidines, styrene, preferably α-methylstyrene, 1,2-epoxy-4-vinylcyclohexane, allyl chloride, alken chloride, preferably allyl chloride, and fluoride It can be selected from the group consisting of alkenes, preferably 4,4,5,5,6,6,7,7,7-nonafluoro-1-heptene.

  The unsaturated compounds can also be selected from compounds comprising several alkene functional groups, preferably two or three alkene functional groups, particularly preferably the following compounds:

And p is a numerical value 1 or 2, and q is a numerical value 2 to 6, preferably 2 or 4.
The unsaturated compounds have the formula (X):
A _g U _h SiO _{(4- (g + h)) / 2} (X)
[In the formula:
The same or different A radicals represent linear or branched alkenyl or alkynyl radicals containing 2 to 6 carbon atoms;
-Identical or different U radicals represent monovalent radicals other than hydrogen atoms;
-G and h represent integers, g is the number 1 or 2, h is the number 0, 1 or 2 and (g + h) is the number 1, 2 or 3]
And optionally the formula (XI):
U _i SiO _{(4-i) / 2} (XI)
[Wherein, U has the same meaning as described above, and i represents an integer of 0 to 3]
It is also possible to select from polyorganosiloxane (usually denoted as POS) compounds containing other units of

  In formulas (X) and (XI), U is a monovalent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms optionally substituted by at least one halogen atom, and an aryl group It can represent a radical. U can conveniently represent a monovalent radical selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.

Examples of polyorganosiloxanes which may be unsaturated compounds are:
-Poly (dimethylsiloxane) with dimethylvinylsilyl end;
-Poly (dimethylsiloxane-co-methylphenylsiloxane) having a dimethylvinylsilyl end;
-Poly (dimethylsiloxane-co-methylvinylsiloxane) having a dimethylvinylsilyl end;
-Poly (dimethylsiloxane-co-methylvinylsiloxane) with trimethylsilyl end; and-cyclic poly (methylvinylsiloxane),
It is.

  According to a particular aspect of the present invention, unsaturated compounds comprising at least one alkene function and / or at least one alkyne function, and compounds comprising at least one hydrosilyl function are, on the one hand, at least one alkene. It can be identical to a compound comprising a functional group and / or at least one alkyne functional group, on the other hand containing at least one silicon atom and at least one hydrogen atom bonded to the silicon atom. Thus, this compound can be described as "bifunctional" and is capable of reacting as such by a hydrosilylation reaction. Thus, the present invention may also relate to a process for the hydrosilylation of a bifunctional compound with itself, said bifunctional compound, while at least one alkene function and / or at least one alkyne function. The process is characterized in that it comprises, on the other hand, at least one silicon atom and at least one hydrogen atom bound to the silicon atom, said method being catalyzed by a metal complex as described above.

Examples of polyorganosiloxanes which may be difunctional compounds are:
-Poly (dimethylsiloxane-co-hydromethylsiloxane-co-vinylmethylsiloxane) having a dimethylvinylsilyl end;
-Poly (dimethylsiloxane-co-hydromethylsiloxane-co-vinylmethylsiloxane) having a dimethylhydrosilyl end; and-poly (dimethylsiloxane-co-hydromethylsiloxane-co-propyl glycidyl ether methylsiloxane) having a trimethylsilyl end
It is.

  In a related matter, when referring to the use of unsaturated compounds and the use of compounds containing at least one hydrosilyl function, one skilled in the art will understand that this means the use of bifunctional compounds.

  The hydrosilylation reaction can be carried out in the solvent or in the absence of a solvent. In another form, one of the reactants, for example the unsaturated compound, can act as a solvent. Suitable solvents are those which are miscible with the compound containing at least one hydrosilyl group.

  The hydrosilylation reaction is carried out at a temperature of 15 ° C. to 300 ° C., preferably 20 ° C. to 240 ° C., more preferably 70 ° C. to 200 ° C., more preferably 50 ° C. to 140 ° C., still more preferably 50 ° C. to 100 ° C. be able to.

Another subject of the invention is the means specifically designed to carry out the hydrosilylation process described above. This means:
At least one unsaturated compound comprising at least one alkene function and / or at least one alkyne function,
At least one compound comprising at least one hydrosilyl (≡Si-H) functional group,
And-catalysts selected from metal complexes which are the subject of the present invention,
And a composition comprising

This composition forms the reaction medium in which the hydrosilylation reaction according to the invention can take place. To do this, the composition can be heated as described above.
The relative amounts of unsaturated compound and the compound containing at least one hydrosilyl functional group can be controlled to ensure the conversion of unsaturated and hydrosilyl functional groups. The molar ratio of Si-H functional groups to alkenes and alkyne functional groups of unsaturated compounds of compounds containing at least one hydrosilyl functional group is preferably 1: 100 to 100: 1, more preferably 1:10 to 10: It is 1. According to one aspect, the molar ratio of the Si-H functional group to the alkene and alkyne functional groups of the unsaturated compound of the compound comprising at least one hydrosilyl functional group is strictly less than 1. In this context, the Si-H functional groups are deficient relative to unsaturated functional groups. According to another aspect, the molar ratio of the Si-H functional group to the alkene and alkyne functional groups of the unsaturated compound of the compound comprising at least one hydrosilyl functional group is strictly greater than 1. Thus, the Si-H functionality is in excess relative to the unsaturated functionality.

  According to the invention, the hydrosilylation reaction is carried out in the presence of catalytic amounts of one or more complexes according to the invention. The term "catalytic amount" is understood to mean less than the molar equivalent of metal, relative to the amount of unsaturation present in the reaction medium. The catalyst concentration in the composition according to the invention can typically be 5 ppm to 10 ppm by weight with respect to the unsaturated reactant. However, quite advantageously, the inventors have found that a particularly low content of the catalyst according to the invention is sufficient to obtain high conversions and high hydrosilylation yields. For this reason, the concentration of the catalyst in the composition according to the invention is very advantageously less than 10 ppm by weight, more preferably less than 5 ppm by weight, more preferably 0.1 parts by weight, relative to the weight of unsaturated reactant. It can be from ppm by weight to 3 ppm by weight, even more preferably from 0.1 ppm by weight to 1 ppm by weight.

  The composition can optionally include additives in addition to the unsaturated compound comprising at least one alkene functional group and / or at least one alkyne functional group and the compound comprising at least one hydrosilyl functional group.

  According to one aspect of the invention, inhibitors or retarders of the hydrosilylation reaction can be added to the composition according to the invention. These compounds are known to those skilled in the art and are commercially available. For example, the following compounds: polyorganosiloxanes substituted by at least one alkenyl, which can optionally be provided in the form of a ring; tetramethylvinyltetrasiloxane, which is particularly preferred; pyridine; organic phosphines and phosphorouss Unsaturated amides; alkyl maleates; and acetylenic alcohols can be described.

The acetylenic alcohols which are the preferred thermal blocking agents for the hydrosilylation reaction (as described for example in US Pat.
(R ′) (R ′ ′) C (OH) -C≡CH
Wherein R ′ is a linear or branched alkyl radical or a phenyl radical, R ′ ′ is a hydrogen atom, a linear or branched alkyl radical or a phenyl radical, as desired The R ′ radical and the R ′ ′ radical as well as the carbon atom located α to the triple bond can form a ring, and the total number of carbon atoms present in R ′ and R ′ ′ is , At least 5, preferably 9 to 20.

Regarding the acetylenic alcohol, as an example:
-1-ethynylcyclohexan-1-ol;
-3-Methyl dodec-1-yn-3-ol;
-3,7,11-trimethyldodec-1-yn-3-ol;
1,1-diphenylprop-2-yn-1-ol;
3-ethyl-6-ethylnon-1-yn-3-ol;
2-methylbut-3-yn-2-ol;
3-methylpentadec-1-yn-3-ol; and-diallyl maleate or diallyl maleate derivative,
Can be described.

The composition of the present invention may further contain conventional functional additives. As a family of conventional functional additives:
-Fillers;
-Adhesion promoters;
-Adhesion modifiers;
-Additives for thermal stability;
-Additives for improving the consistency;
-Pigments;
Additives for thermal stability, oil stability or fire stability, eg metal oxides,
Can be described.

The optionally provided filler is preferably inorganic. These can in particular be silica-based fillers. With respect to silica-based materials, they can act as reinforcing or semi-reinforcing fillers. The reinforcing silica-based filler is selected from colloidal silica, fumed silica or precipitated silica powder, or mixtures thereof. These powders are generally an average particle size smaller than 0.1 [mu] m, BET specific surface area greater than ^{30 m} 2 / g, preferably from 30~350m ² / g. Semi-reinforcing fillers such as diatomaceous earth or ground quartz can also be used. With respect to non-silica based inorganic materials, they can be included as semi-reinforcing or bulking inorganic fillers. Examples of these non-silica based fillers, which can be used alone or as a mixture, are carbon black, titanium dioxide, aluminum oxide, aluminum hydrate, expanded vermiculite, non-expanded vermiculite, optionally surface-treated with fatty acids Calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulfate, and slaked lime. These fillers generally have a particle size distribution of 0.001 to 300 μm and a BET specific surface area of less than 100 m ² / g. Although not limiting, in practice the filler used can be a mixture of quartz and silica. The filler can be treated with a suitable product. In terms of weight, it is preferred to use fillers in an amount of 1% to 50% by weight, preferably 1% to 40% by weight, based on the total components of the composition.

More generally, quantitatively, the composition according to the invention can exhibit a standard ratio in the considered technical field where it is known that application to the target also needs to be considered.
Apart from hydrosilylation, the metal complexes which are the subject of the present invention are coupling reactions, in particular: Heck reaction, Suzuki reaction, amination of aryl halides, α-arylation of amides, Sonogashira coupling, Kumada coupling It can also be used as a catalyst for reactions selected from the group consisting of Stille reactions, and alkyne coupling reactions. For the recording, the Heck reaction is the coupling of an unsaturated halogenated derivative, in particular a halogenated aryl or unsaturated triflate, with an alkene; the Suzuki reaction is between two aryl groups, in particular a boronic acid and a halogenide. Coupling with derivatives; Sonogashira coupling is a direct coupling reaction of aryl halides or vinyl halides with terminal alkynes; Kumada coupling is alkyl aryl or aryl Grignard reagents with aryl halides or halides Stille reaction is the coupling of an organotin compound with a halide. Alkyne coupling reactions are particularly useful for furan synthesis.

Furthermore, the metal complexes which are the subject of the present invention can also be used as catalysts for the metathesis reaction of olefins. The metathesis of olefins consists of the cleavage of the double bond of the alkene, followed by the redistribution of the formed alkylidene fragment. In reactions using olefin metathesis:
Polymerization reactions, such as ring opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization;
-Intramolecular coupling reaction, eg ring closing metathesis (RCM);
-Intramolecular coupling reactions, such as cross metathesis (CM) coupling,
Can be described.

  The metal complexes which are the subject of the present invention are hydrogenations of alkenes and arenes as catalysts for polymerization reactions, such as copolymerization of ethylene and carbon monoxide to form polyketones and electron transfer radical polymerization (ATRP). And as catalysts for hydroformylation, as catalysts for the dehalogenation of aryl halides, as catalysts for cyclopropanation of olefins with diazoalkanes, or, in particular, arylation and alkenylation of aldehydes with boronic acid derivatives Can also be used as a catalyst for

Another subject of the present invention is any one of the above-mentioned reactions characterized in that it is catalyzed by the metal complex which is the subject of the present invention.
The use of the metal complexes according to the invention as catalysts is particularly advantageous when the catalyzed reaction is an asymmetric synthesis reaction.

  Other objects, features and advantages of the present invention will become apparent from the following examples, which are given purely by way of illustration and not limitation.

  Example 1: Synthesis of silylene ligand 1

Step 1: Synthesis of chlorophosphine (a)

151.3 ml (242.08 mmol) of n-BuLi (1.6 M) in a solution of Me ₂ Si (NHt-Bu) ₂ (24.50 g; 121.04 mmol) in 80 ml of toluene at −78 ° C. Added. After returning to ambient temperature, the solution was heated at 50 ° C. for 4 hours. A solution of PCl ₃ (11.7 ml; 133.14 mmol) in 30 ml of toluene was cooled to -110 ° C and the above solution was added dropwise, with absolutely no temperature above -100 ° C. The solution was allowed to return to ambient temperature overnight. The solvent is evaporated under vacuum and the residue is taken up with 150 ml of pentane. The filtration was done and chlorophosphine (a) was extracted twice with 100 ml of pentane. The pentane was evaporated under vacuum and purification was carried out by distillation under vacuum to give a colorless oil (18.27 g, yield: 56.6%).

Step 2: Synthesis of imine (b)

  2,6-diisopropylaniline (85.3 ml; 481.34 mmol) and a catalytic amount of p-toluenesulfonic acid were added to a solution of norcamphor (53.02 g; 481.34 mmol) in 200 ml of toluene. The mixture was heated in a Dean-Stark apparatus at 135 ° C. for 72 hours. The solvent was evaporated and the solid was collected with pentane. The solution was then concentrated and allowed to crystallize overnight at -30 <0> C. The imine (b) was obtained in the form of slightly brown crystals (119.22 g; yield: 92.0%).

Step 3: Synthesis of iminophosphine (c)

  44.9 ml (71.79 mmol) of n-BuLi (1.6 M) are added to a solution of imine (b) (18.40 g; 68.38 mmol) in 150 ml of THF at -78 ° C. and the mixture Returned to ambient temperature. After stirring for 1 hour, the solution was cooled again to -78 ° C and chlorophosphine (a) (18.23 g; 68.38 mmol) was added. The mixture was allowed to return to ambient temperature and the solvent was evaporated under vacuum. The solid was taken up with 120 ml of pentane and filtered. Extraction was carried out three times with 50 ml of pentane. The product was then purified by washing three times with 40 ml of acetonitrile to give a white solid (24.25 g; yield: 71.0%).

Step 4: Synthesis of phosphino-N-silylene amine (d)

9.8 ml (15.71 mmol) of n-BuLI (1.6 M) are added to a solution of iminophosphine (c) (7.85 g; 15.71 mmol) in 80 ml of THF at -78 ° C. The mixture was allowed to return to ambient temperature. After stirring for 1 hour, the solution was cooled again to -78 ° C and 1 equivalent of SiHCl ₃ (1.6 ml; 15.71 mmol) was added. The mixture is allowed to return to ambient temperature with stirring for 1 hour and then the solvent is evaporated under vacuum. The solid was collected with 60 ml of pentane and filtered. Extraction was carried out twice with 40 ml of diethyl ether. The solution was concentrated and allowed to crystallize at -30 ° C. Light yellow crystals were obtained (7.81 g; yield: 83.0%).

Step 5: Synthesis of hydrosilylene (e)

  Magnesium powder (130 mg; 5.35 mmol) was added to a solution of compound (d) (2.46 g; 4.10 mmol) in 80 ml of THF. After stirring overnight at ambient temperature, the solvent is evaporated off under vacuum and the residue is taken up with 40 ml of pentane. The solution was filtered and the silylene (e) was extracted twice with 40 ml of pentane. After evaporation of the solvent, the residue is extracted twice with 3 ml of cold pentane to give analytically pure silylene (e) in the form of a pale yellow solid (1.52 g; yield: 70.2%).

Step 6: Synthesis of silylene ligand 1

  Diphenylacetylene (1.58 mmol) was added at ambient temperature to a solution of compound (e) (0.83 g, 1.58 mmol) in toluene (5 ml). The solution was heated to 80 ° C. After 15 hours at 80 ° C., all volatile compounds were removed under vacuum. After washing the residue with pentane (7 ml), silylene compound 2 was obtained in the form of a white solid (0.96 g, 81%).

Melting point = 175-176 ° C (decomposition).
Product 1 is composed of two isomers: 92% major isomer and 8% minor isomer.

Characterization of Main Product 1:
¹ H NMR (300.18 MHz, C ₆ D ₆ , 25 ° C.): δ = −0.12 (s, 3 H, CH 3 _Si ), 0.14 (s, 3 H, CH 3 _Si ), 1.04 (br d _{, J HH = 8.9Hz, 1H,} 1 / 2CH 2Norb), 1.16 (s, 9H, 3 × CH 3tBu), 1.23 (d, J HH = 6.6Hz, 3H, CH 3iPr), 1 _{.24 (d, J HH = 6.8Hz} , 3H, CH 3iPr), 1.29 (d, J HH = 6.9Hz, 3H, CH 3iPr), 1.33 (s, 9H, 3 × CH 3tBu) , 1.32 (a signal with methyl, 1 H, 1/2 CH 2 _{Cbridgehead CP} ), 1. ₄₄ (m, 1 H, 1/2 CH 2 _{Cbridgehead CP} ), 1.55 (m, 1 H, 1/2 CH 2 _{Cbridgehead CN} ), 1.62 (m, 2H, 1/2 CH 2 _{Cbridgehead CN} , 1/2 CH 2 _Norb ), 1.71 (d, J _HH = 6.8 Hz, 3 H, CH 3 _iPr ), 2.46 (s, 1 H, PCCH _bridgehead ), 3.11 (s, 1 H, NCCH _bridgehead ), 3. ₃₆ (sep, J _HH = 6.8 Hz, 1 H, CH _iPr ), 3.57 (d, J _PH = 30.8 Hz, 1 H, SiCH) _{, 3.67 (sep, J HH =} 6.9Hz, 1H, CH iPr), 6.60-7.20 (11H, H Ar), 7.85ppm (br, 2H, H Ar).
¹³ C { ¹ H} NMR (75.47 MHz, C ₆ D ₆ , 25 ° C.): δ = 2.2 (d, J _PC = 2.3 Hz, CH 3 _Si ), 4.6 (br s, CH 3 _Si ) , 22.00 (s, _CH3iPr ), 22.8 (s, _CH3iPr ), 23.7 (s, _{CH2CbridgeheadCP} ), 24.5 (s, _CH3iPr ), 25.4 (s, _CH3iPr ) _{, 26.9 (s, CH iPr)} , 27.4 (s, CH 2CbridgeheadCN), 27.5 (s, CH iPr), 31.4 (d, J PC = 4.6Hz, 3C, 3 × CH 3tBu ), 32.0 (d, J _PC = 4.3 Hz, 3 C, 3 × CH 3 _{t Bu} ), 35.5 (s, SiCH), 42.7 (d, J _PC = 9.3 Hz, NCCH _bridgehead ), 45 .2 ( _{, J PC = 68.8Hz, PCSi)} , 45.3 (d, J PC = 8.9Hz, CH 2Norb), 45.7 (d, J PC = 10.0Hz, PCCH bridgehead), 50.5 (d _{, J PC = 1,1Hz, C tBu} ), 50.9 (br s, C tBu), 84.3 (d, J PC = 129.7Hz, PC = CN), 121.1 (s, CH Ar) , 122.7 (s, CH _Ar ), 123.1 (s, CH _Ar ), 125.1 (d, J _PC = 2.5 Hz, CH _Ar ), 125.5 (s, 2 x CH _Ar ), 126.0 (s, CH _Ar ), 126.4 (s, 2 x CH _Ar ), 126.9 (s, 2 x CH _Ar ), 136.0 (br, 2 x CH _Ar ), 136.5 ( _{d, J PC = 2.8Hz, C} Ar), 140.3 (d, J _{C = 0.5Hz, C Ar),} 143.5 (s, C Ar), 145.3 (d, J PC = 1.4Hz, C Ar), 147.3 (s, C Ar), 172.9ppm (D, J _PC = 9.8 Hz, PC = CN).
²⁹ Si { ¹ H} NMR (59.63 MHz, C ₆ D ₆ , 25 ° C.): δ = -87.4 (d, J _PSi = 2.9 Hz, Si _CP ), 7.2 ppm (s, Si _Me ) .
³¹ P { ¹ H} NMR (121.49 MHz, C ₆ D ₆ , 25 ° C.): δ = 46.5 ppm (s).
Characterization of minor product 1:
¹ H NMR (300.18 MHz, C ₆ D ₆ , 25 ° C.): δ = 3.02 (d, J _PH = 31.1 Hz, 1 H, Si 2 _{CH 3} ).
¹³ C { ¹ H} NMR (75.47 MHz, C ₆ D ₆ , 25 ° C.): δ = 36.4 (s, Si _{CH 3} ).
³¹ P { ¹ H} NMR (121.49 MHz, C ₆ D ₆ , 25 ° C.): δ = 42.8 ppm (s).
Example 2: Synthesis of metal complex containing silylene ligand 2

  A solution of platinum (0) (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) complex in xylene (1.2 ml; 0.11 mmol) was added to product 1 (150 mg; 0.21 mmol). ) At ambient temperature. After mixing for 2 hours, all volatile compounds were removed under vacuum and the solid was washed with pentane to give analytically pure product 2 in the form of a white powder (152 mg, 70%). Crystals of product 2 suitable for X-ray diffraction analysis were obtained from dichloromethane / pentane solution at ambient temperature.

Product 2 is composed of two isomers: 94% of the main isomer and 6% of the minor isomer.
The metal complex 2 thus obtained is stable in air.

Characterization of Main Product 2:
¹ H NMR (300.18 MHz, CDCl ₃ , 25 ° C.): δ = −0.65 (s, 3 H, CH 3 _Si ), _−0.43 (s, 3 H, CH 3 _Si ), − 0.23 (s, _{3H, CH 3Si), 0.16 (} s, 3H, CH 3Si), 0.36 (s, 3H, CH 3Si), 0.55 (s, 3H, CH 3Si), 0.86 (d, J HH _{= 6.6Hz, 3H, CH 3iPr)} , 0.97 (br s, overlapping with _{CH 3iPr, 1H, H 2 CCH} ), 0.99 (d, J HH = 6.6Hz, 3H, CH 3iPr), 1 _{.10 (br s, 1H, 1} / 2H 2 CCH), 1.28 (d, J HH = 6.6Hz, 3H, CH 3iPr), 1.29 (d, J HH = 6.6Hz, 3H, CH _{3iPr), 1.36 (br d,} 1H, 1 / 2CH 2Norb _, 1.50 _(CH 3tBu _{duplicates, 1H, PCCH bridgehead), 1.51} (s, 9H, 3 × CH 3tBu), 1.53 (CH 3tBu _{duplicates, 1H, 1 / 2H 2 CCH} ), 1. 56 (s, 9 H, 3 x CH 3 _{t Bu} ), _{1. 66} (br s, 1 H, CH 2 _{Cbridgehead CP} ), _{1. 67} (br s, 1 H, H ₂ CCH), 1.74 (br d, 1 H, _1/1 2CH 2 _Norb ), 1.84 (br d, 2 H, CH 2 _{Cbridgehead CN} ), 2.59 (d, J _HH = 13.5 Hz, 1 H, 1/2 H ₂ CCH), 2.63 (s, 1 H, PCCH _bridgehead ) _{, 2.99 (d, J HH =} 11.4Hz, 1H, 1 / 2H 2 CCH), 3.06 (m, 1H, CH iPr), 3.34 (m, 1H, C _{iPr), 3.38 (d, J} PH = 31.8Hz, 1H, SiCH), 3.48 (s, 1H, NCCH bridgehead), 6.33 (m, 2H, H Ar), 6.73 (m _{, 3H, H Ar), 6.80-7.12} (6H, H Ar), 7.51ppm (br, 2H, H Ar).
¹³ C { ¹ H} NMR (75.47 MHz, CDCl ₃ , 25 ° C.): δ = −1.8 (s, CH 3 _Si ), −1.5 (s, CH 3 _Si ), 1.6 (s, CH _{3Si), 1.7 (s, CH} 3Si), 3.1 (d, J PC = 1.5Hz, CH 3Si), 6.0 (br s, CH 3Si), 23.5 (s, CH 3iPr) _{, 24.3 (s, CH 3iPr)} , 25.5 (s, CH 2CbridgeheadCP), 26.2 (s, CH 3iPr), 26.6 (s, CH 3iPr), 27.7 (s, CH iPr) , 28.2 (s, CH 2 _{Cbridgehead CN} ), 28.9 (s, CH _iPr ), 32.4 (d, J _PC = 4.5 Hz, SiCH), 32.7 (d, J _PC = 5.2 Hz, 3C, 3 x CH _3tBu ), 33.2 (D, J _PC = 4.5 Hz, 3 C, 3 × CH 3 t _Bu ), 36.0 (t, J _Pt C = 51.0 Hz, 2 C, 2 × H ₂ CCH), 41.0 (s, H ₂ CCH) , 41.4 (s, H ₂ CCH), 43.9 (d, J _PC = 8.7 Hz, NCCH _bridgehead ), 47.0 (d, J _PC = 9.7 Hz, PCCH _bridgehead ), 42.5 ( _{d, J PC = 125.2Hz, PCSi} ), 47.1 (d, J PC = 9.0Hz, CH 2Norb), 52.1 (s, C tBu), 52.5 (d, J PC = 1. 5 Hz, C _tBu ), 87.8 (d, J _PC = 121.5 Hz, PCCN), 122.4 (s, CH _Ar ), 123.8 (s, CH _Ar ), 123.9 (s, CH _Ar) ), 126.0 (d, J _PC = 3 Hz) , CH _Ar ), 126.2 (s, 2 x CH _Ar ), 126.2 (s, CH _Ar ), 126.3 (s, CH _Ar ), 127.0 (s, CH _Ar ), 129.8 (S, 2 x CH _Ar ), 134.0 (d, J _PC = 4.5 Hz, C _Ar ), 136.7 (d, J _PC = 7.5 Hz, 2 x CH _Ar ), 140.3 (s , C _Ar ), 142.2 (s, C _Ar ), 146.6 (s, C _Ar ), 148.0 (s, C _Ar ), 175.8 ppm (d, J _PC = 9.4 Hz, PCCN) .
²⁹ Si { ¹ H} NMR (59.63 MHz, CDCl ₃ , 25 ° C.): δ = −24.4 (s, SiPt), 2.4 ppm (s, SiMe), 3.4 ppm (s, SiMe), 10 .4 ppm (d, J _PSi = 1.8 Hz, SiMe).
³¹ P { ¹ H} NMR (121.49 MHz, CDCl ₃ , 25 ° C.): δ = 48.5 ppm (d, J _PPt = 14.6 Hz).
¹⁹⁵ Pt { ¹ H} NMR (107.55 MHz, CDCl ₃ , 25 ° C.): δ = 5968.7 ppm (s).
Characterization of the minor product 2:
³¹ P { ¹ H} NMR (121.49 MHz, CDCl ₃ , 25 ° C.): δ = 43.1 ppm (s).
¹⁹⁵ Pt { ¹ H} NMR (107.55 MHz, CDCl ₃ , 25 ° C.): δ = 5966.6 ppm (s).
Example 3: Hydrosilylation of 1-octene with bis (trimethylsiloxy) methyl hydrosilane catalyzed by a platinum complex having a silylene ligand

In this example, the product 2 obtained in Example 2 was used as a catalyst.
A xylene solution containing different concentrations of product 2 was prepared: A 0.005 M solution was obtained by dissolving 26 mg (0.025 mmol) of product 2 in 5 ml of xylene. 0.0005 M and 0.00005 M solutions were prepared by diluting 0.1 ml of the first solution to 1 ml and 10 ml, respectively.

  A solution of 1-octene (1.85 mmol), bis (trimethylsiloxy) methylhydrosilane (1.85 mmol), and the catalyst in xylene was mixed and the combination was heated at 72 ° C. with stirring. The reaction was monitored by proton NMR and gas chromatography. At the end of the reaction, all volatile compounds were removed under vacuum and pentane was added. After filtration, the solvent was evaporated under vacuum.

At the completion of the reaction, the conversion of the reaction and the yield were determined by proton NMR and gas chromatography.
Several tests were performed with varying concentrations of catalyst. In addition, a comparative test was performed using Karstedt platinum complex (Pt ₂ (DVTMS) ₃ ) as a catalyst. The results are given in Table 1.

The concentration of catalyst is expressed in mol% and wt% relative to 1-octene.
Using product 2 as catalyst, it was found that high conversion of hydrosilylation was obtained even at very low concentrations, on the order of 2.5 × 10 ⁻⁴ wt%. Platinum complexes with silylene ligands were able to obtain high rates of conversion when using very low concentrations of catalyst compared to Karstedt's catalyst.

Claims (10)

A metal complex comprising at least one Pt atom and one or more ligands, wherein the at least one ligand donates an electron pair to a cyclic silylene structure which is silacyclopropylidene and a silicon atom of the cyclic silylene structure. And the cyclic silylene structure is represented by the formula (V) :

Compounds of the formula
Each R ^b is independently:
-Hydrogen atom ;
An alkyl group which may be substituted by one or more halogen atoms or an alkoxy group;
-A cycloalkyl group which may be substituted by one or more halogen atoms, an alkyl group, a haloalkyl group or an alkoxy group;
-A cycloalkylalkyl group in which the cycloalkyl moiety and / or the alkyl moiety may be substituted with one or more halogen atoms, an alkyl group, a haloalkyl group, or an alkoxy group;
-An aryl group which may be substituted by one or more halogen atoms, an alkyl group, a haloalkyl group, a cycloalkyl group or an alkoxy group;
-An arylalkyl group which may be substituted by one or more halogen atoms, an alkyl group, a haloalkyl group, a cycloalkyl group, or an alkoxy group;
It is selected from;
Each R ^e is independently: a hydrogen atom; a halogen atom; or an alkyl group optionally substituted with one or more halogen atoms and / or an alkyl group, a haloalkyl group, a cycloalkyl group; a cycloalkyl moiety and / or Or a cycloalkylalkyl group wherein the alkyl moiety may be substituted with one or more halogen atoms and / or an alkyl group; an aryl group optionally substituted with one or more halogen atoms and / or an alkyl group; an aryl moiety and / or Or an arylalkyl group wherein the alkyl moiety may be substituted by one or more halogen atoms and / or an alkyl group; an acyl group; and a group selected from a hydroxyl group,
Alternatively, two or more groups selected from R ^e group and R ^b group, together with the atoms to which they are attached, may contain one or more unsaturation and are selected from O, N, Si, and P A monocyclic or polycyclic 3-20 membered ring group may be formed, which may contain one or more hetero atoms, and the monocyclic or polycyclic ring is one or more halogen atoms, It may be substituted by an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an arylalkyl group, an acyl group, an amine group, a hydroxyl group or an alkoxy group,
Said metal complex. Metal complex according to claim 1, characterized in that it comprises one or more other ligands selected from mono- and di-olefins. A ligand comprising a cyclic silylene structure and a Lewis base which donates an electron pair to a silicon atom of the cyclic silylene structure is a compound of the formula (VI):

[Wherein the symbol “Q” is

And the symbol "Ary" is

Represents
The metal complex according to claim 1 or 2 , which is a compound of The metal complex is represented by formula (VII):

[Wherein the symbol “Q” is

And the symbol "Ary" is

Represents
The metal complex according to any one of claims 1 to 3 , which is a compound of Use of the metal complex according to any one of claims 1 to 4 as a catalyst. 6. Use according to claim 5 , characterized in that metal complexes are used as catalysts for hydrosilylation reactions. 5. A method of hydrosilylating an unsaturated compound comprising at least one alkene functional group and / or at least one alkyne functional group with a compound comprising at least one hydrosilyl functional group, the method as claimed in any one of claims 1 to 4 C., which is catalyzed by the metal complex described in 1. above. Compounds containing at least one hydrosilyl function are:
A silane or polysilane compound comprising at least one hydrogen atom bonded to a silicon atom;
A siloxane compound comprising at least one hydrogen atom bonded to a silicon atom;
-An organic polymer containing hydrosilyl functional groups at the end position;
The method of claim 7 , wherein the method is selected from the group consisting of At least one unsaturated compound comprising at least one alkene function and / or at least one alkyne function,
-A catalyst selected from at least one compound comprising at least one hydrosilyl function, and-a metal complex according to any one of claims 1 to 4 ;
A composition comprising: The composition according to claim 9 , characterized in that the concentration of catalyst in the composition is less than 10 ppm by weight relative to the weight of unsaturated reactant.